Chemical reactions of chromium and vanadium in graphite furnace atomic absorption spectrometry

The chemical reactions of V and Cr in the graphite furnace are determined by absorption measurements, X-ray diffraction and electron microscopy techniques. It is shown that both elements form carbides, VC and Cr₃C₂, respectively. An increase in absorption is obtained in tubes coated with pyrolytic graphite. Interferences of carbideforming elements on the absorption signal are studied. Reaction paths are proposed for both elements during their heat treatment in graphite furnace AAS.     

Determination of boron in river water with flameless atomic absorption spectrometry (graphite furnace technique)

Summary A simple and rapid procedure is described for the determination of boron in water using flameless atomic absorption spectrometry. A Ca/Mg solution is added before measurement. The method is suitable for boron concentrations up to 250 g/l. The mean standard deviation is 6±4 g/l.

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Bestimmung von Bor in Flußwasser mittels flammenloser Atomabsorptions-Spektrometrie (Graphitrohrtechnik)

Zusammenfassung Eine schnelle und einfache Methode zur Bestimmung von Bor im Wasser mittels flammenloser AAS wird beschrieben. Die Messung erfolgt nach Zugabe einer Ca/Mg-Lösung. Die Methode ist geeignet für Borkonzentrationen bis 250 g/l. Die mittlere Standardabweichung beträgt 6±4 g/l.

     

Application of standardless analysis in graphite furnace atomic absorption spectrometry: determination of chromium

Influences of atomization temperatures on the characteristic mass and the atomic absorption coefficient of chromium were studied. The experimental results show that the values of characteristic mass have appeared to be stable to better than 10% when the analyte is atomized in the range of 2500-2800 degrees. The standardless analysis was applied to the determination of chromium in standard sediment and geochemical reference samples and satisfactory results were obtained.     

Effect of matrix components on chromium atomization processes in graphite furnace atomic absorption spectrometry

The effect of various organic and inorganic matrix components on chromium atomization in graphite furnace atomic absorption spectrometry is studied. The results are explained on the basis of chromium's atomization mechanisms. The two predominant mechanisms are the thermal dissociation of the oxide and of the carbide. Losses through molecular volatilization reduce the sensitivity when chromium chelate complexes are atomized. In this case, the atomization mechanism consists of the thermal dissociation of the chelate. The formation of chromium carbide from the carbon residue produced by decomposition of the organic solvents leads to a loss of sensitivity.     

Non-spectral interferences in flameless atomic absorption spectrometry using graphite mini-tube furnaces

This work concerns non-spectral interferences occurring in flameless atomic absorption spectrometry using a Varian Techtron CRA model 63 instrument. Special attention has been paid to the influence exerted by concomitants on the vaporization and atomization behaviour of the test elements Be, Mn and Zn. Tracer analysis permitted the direct determination of the vaporization patterns of the test elements during the atomization phase. The variation of the transient absorption signals with time was measured using an electronic recording system sufficiently fast to obtain instrumentally undistorted pulses. The concomitants were selected on the basis of literature dealing with thermochemical processes in are emission spectrometry. Results are discussed on the basis of (i) the decrease of the content of the test element in the furnace, (ii) the characteristics of the absorption signal, and (iii) the surface temperature of the furnace. It turned out that the class “atomization efficiency interferences” might constitute one of the most serious sources of systematic error in frameless atomic absorption spectrometry.     

Influence of the shape of the graphite furnace on wall and gas temperatures and analytical performance in graphite furnace atomic absorption spectrometry

Summary A brief outline is given of a model for numerical calculation of the dynamic wall and gas temperature distributions of a graphite furnace atomiser of the Massmann type. Results for the standard as well as contoured furnaces are presented. Shaped furnaces feature gas temperatures higher than the wall temperature at the tube centre over a considerable volume. A contoured furnace designed to achieve stabilized temperature conditions was evaluated with respect to matrix effects for four elements in six matrices. A limited degree of improvement in analytical performance was found for this furnace as well as for the platform-in-tube technique.

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Einfluß der Form des Graphitofens auf die Wand- und Gastemperatur und analytische Leistungsfähigkeit in der Graphitofen-AAS

Zusammenfassung Ein Modell zur numerischen Berechnung der dynamischen Wand- und Gastemperaturverteilung eines Graphitofen-Atomisers vom Maßmann-Typ wird beschrieben. Ergebnisse für Standard- und konturierte Öfen werden vorgestellt. Geformte Öfen weisen Gastemperaturen auf, die über ein beträchtliches Volumen höher sind als die Wandtemperatur im Rohrzentrum. Ein für stabilisierte Temperaturbedingungen entwickelter konturierter Ofen wurde in bezug auf die Matrixeffekte für vier Elemente in sechs Matrices ausgewertet. Eine begrenzte Verbesserung der analytischen Leistungsfähigkeit wurde für diesen Ofen wie auch für die Plattform-Methode gefunden.

     

石墨炉原子吸收光谱法测定中药口服液中的铬铅镉

利用石墨炉原子吸收光谱法测定,采用常温消解和密闭微波消解等方式处理口服液样品,并进行比较。结果表明,采用HNO3 HClO4 H2O2作为消解试剂用常温消解方式进行消解后,可不加基体改进剂直接进行测定,在此基础上研究了石墨炉原子吸收测定的最佳条件。应用这种方法测定了双黄连、清开灵、生脉饮和抗病毒口服液中痕量镉、铬和铅,RSD小于5．0％,回收率在83．4％～113％。     

Slurry sampling for graphite furnace atomic absorption spectrometry

Summary Slurry preparations are an effective way to introduce solids into the graphite furnace. Ultrasonic agitation keeps samples mixed prior to analysis. Several aspects of the ultrasonic slurry sampling approach are discussed including contamination concerns, analyte partitioning, and the effect of particle size. In addition, sample preparation strategies for slurry preparations of non-powdered materials are reviewed. The suitability of this method for assessing homogeneity is demonstrated.     

Latest innovations in graphite furnace atomic absorption spectrometry technique

An overview of the latest innovations in the graphite furnace atomic absorption spectrometry technique is described. The use of the transverse heated graphite atomizer technology with its huge advantages, the possibilities of running powdered solids through the slurry technique, and the future possibility of using flow injection on-line with the graphite furnace are mentioned.     

Advances in ultrasonic slurry graphite furnace atomic absorption spectrometry

Summary Ultrasonic slurry graphite furnace atomic absorption spectrometry is a useful technique for automated direct analysis of solids. The effectiveness of ultrasonic agitation for mixing samples is demonstrated. This analytical approach is evaluated to identify sources of imprecision. Strategies for optimizing slurry preparations are discussed, focusing on particle size, density, analyte partitioning, and sampling limitations. Finally, a teflon bead method is presented for grinding biological and botanical samples. An optimized general approach for ultrasonic slurry sampling is presented.Presented at the 5th International Colloquium on Solid Sampling with Atomic Spectroscopy, May 18–20, 1992; Geel, Belgium. Papers edited by R. F. M. Herber, Amsterdam.     

Speciation of chromium in mineral waters and salinas by solid-phase extraction and graphite furnace atomic absorption spectrometry

A simple GF-AAS method for speciation analysis of chromium in mineral waters and salinas was developed. Cr(VI) species were separated from Cr(III) by solid-phase extraction with APDC (ammonium pyrrolidinedithiocarbamate). The APDC complexes were formed in the sample solution under proper conditions, adsorbed on Diaion HP-2MG resin and the resin was separated from the sample. After elution with concentrated nitric acid Cr(VI) was determined by GF-AAS. Total chromium was determined by GF-AAS directly in the sample and Cr(III) concentration was calculated as the difference between those results.

The detection limit of the method defined as 3 s of background variation was 0.03 μg l⁻¹ for Cr(VI) and 0.3 μg l⁻¹ for total chromium. RSD for Cr(VI) determination at the concentration of 0.14 μg l⁻¹ was 9%, and for total chromium at the concentration of 5.6 μg l⁻¹ was 5%. The recovery of Cr(VI) was in the range of 94–100%, dependently on type of the sample.

The investigation of recovery of the spiked Cr(VI) showed that at concentration levels near 1 μg l⁻¹ and lower recovery may be reduced significantly even by pure reagents that seem to be free from any reductants.     

Pigment identification in artwork using graphite furnace atomic absorption spectrometry

The use of a sampling technique is described for the identification of metals from inorganic pigments in paint. The sampling technique involves gently contacting a cotton swab with the painted surface to physically remove a minute quantity (∼1-2 μg) of pigment. The amount of material removed from the painted surface is invisible to the unaided eye and does not cause any visible effect to the painted surface. The cotton swab was then placed in a 1.5 ml polystyrene beaker containing HNO₃ to extract pigment metals prior to analysis using graphite furnace atomic absorption spectrometry (GFAAS). GFAAS is well suited for identifying pigment metals since it requires small samples and many pigments consist of main group elements (e.g. Al) as well as transition metals (e.g. Zn, Fe and Cd). Using Cd (cadmium red) as the test element, the reproducibility of sampling a paint surface with the cotton swab was approximately 13% in either a water or oil medium. To test the feasibility of cotton sampling for pigment identification, samples were obtained from paintings (watercolour and oil) of a local collection. Raman spectra provided complementary information to the GFAAS, which together are essential for positive identification of some pigments. For example, GFAAS indicated the presence of Cu, but the Raman spectra positively identified the modern copper pigment phthalocyanine green (Cu(C₃₂Cl₁₆N₈). Both Raman spectroscopy and GFAAS were useful for identifying ZnO as a white pigment.     

Determination of traces of chromium in cocaine and heroin by flameless atomic absorption spectrometry

A method for the determination of total chromium in cocaine and heroin by flameless atomic absorption spectrometry is presented. Cocaine samples were dissolved in 2 ml of HNO(3) 35.0% (v/v) and diluted to 10 ml with ultrapure water; heroin samples were dissolved in ultrapure water, adding 0.4 ml of HNO(3) 35.0% (v/v) to dissolve inert species, and also diluted to 10 ml. Mg(NO(3))(2) and HNO(3), as chemical modifiers, were compared in terms of sensitivity, precision and accuracy, a lower detection limit being obtained for the use of Mg(NO(3))(2), 5.77 mug kg(-1) (7.23 mukg(-1) for HNO(3)). Within-batch precision was found to be 6.19% and 1.48% for drug solution spiked with 0 and 10 mug l(-1) of Cr(3+), respectively, when using Mg(NO(3))(2), and 7.45 and 1.19% for the same respective concentration levels when using HNO(3). Similar results on analytical recovery were obtained for both Mg(NO(3))(2) and HNO(3). Mg(NO(3))(2) was selected as the more adequate of the two chemical modifiers. A study of the introduction of a cooling-down step of 50 degrees C was carried out and compared in terms of sensitivity to the programme without a cooling-down step, but no advantage was observed. Studies on the variation in precision and analytical recovery with the amount of sample, and interferent effects of different species on chromium determination were developed. Finally, chromium concentrations obtained in cocaine samples varied between 0.02 and 0.14 mg kg(-1), the levels in the heroin samples being in the 0.05-0.59 mg kg(-1) range.     

Determination of the temperature of the graphite probe surface in graphite probe furnace atomic absorption spectrometry

An apparatus for determining the temperature of a graphite probe in graphite probe furnace atomic absorption spectrometry has been developed and tested. By measuring the change in the reflection of a laser beam from various pure metals which are deposited on the probe surface at the usual location for sample deposition, it has been found that the heating of the graphite probe surface occurs in two stages. When the probe is inserted into a pulse-heated, commercial graphite furnace after it has been heated to a steady-state temperature, the probe surface is initially rapidly heated by the radiation from the heated graphite tube wall, and thereafter the probe maintains that steady-state temperature for a short time. For a given graphite probe, the heating rate at the initial stage and the corresponding steady-state temperature at the final stage are mainly determined by the final tube wall temperature; the steady-state temperature of the probe is considerably lower than the final tube wall temperature because of thermal conduction by the probe to that part of its body which is lying outside the tube wall. The higher the final tube wall temperature, the higher is the heating rate of the probe at the initial stage, the higher is its steady-state temperature at the final stage, and the less is the difference between the final tube wall temperature and the steady-state temperature of the probe surface. The heating rate of the probe surface at 1600 K is 180 K s⁻¹, whereas at 2300 K it is 3600 K s⁻¹; the differences between the probe surface and tube wall temperatures at the former temperature is 700 K, whereas at the latter temperature it is 250 K.     

石墨炉原子吸收光谱法测定茶叶中的铅

采用石墨炉原子吸收光谱法测定茶叶中铅,以NH4H2PO4作为基体改进剂,提高了测定的灰化温度,消除了基体干扰.方法简便,快速,准确度高.通过对标准物质的多次测定,结果均在其保证值范围内,相对标准偏差为2.8%.对样品进行加标回收试验,回收率为96%～105%,方法检出限为0.12μg/L.     

Determination of molybdenum in plasma using graphite furnace atomic absorption spectrometry

A sensitive method is described for the determination of Mo in plasma or serum by graphite furnace atomic absorption spectrometry. The method involves extraction of the metal as the 8-hydroxyquinoline complex and is free of the interference effects that prevent the direct analysis of plasma for Mo. Recoveries of internal standards were excellent and results from the analysis of a National Institute of Standards and Technology Standard Reference Material were in good agreement with certified values. The sensitivity of the method, based on the analysis of 1 ml of plasma, is ca. 3 ng ml-1.     

Condensation of analyte vapor species in graphite furnace atomic absorption spectrometry

A shadow spectral digital imaging technique (SSDI) with charge coupled device (CCD) camera detection was used to investigate the spatial and temporal distribution of condensation clouds of analyte species generated in a graphite furnace during the atomization of 5–40-μg masses of metals. Complex, non-uniform structures of aerosol species located away from both the graphite tube axis and walls are prevalent. Species giving rise to observed signals are likely clusters of metals in the case of Ag, Au and Pd, and oxide aerosols for elements such as Al, Ca and Mg. Source scatter often arises during the atomization of relatively large masses of analytes (or during the atomization of real samples containing high concentrations of concomitant matrix species) in the graphite furnace due to such aerosol formation. The SSDI technique is an extremely useful aid to the elucidation of this phenomenon and imaging at several wavelengths using both line and continuum sources in combination with (thermal, incandescent) emission from these structures permits a more complete picture to be developed.